(meth)acrylate and use thereof

Abstract

It is an object of the present invention to provide a monomer which can provide a cured product having both high toughness and rigidity. The present invention is a (meth)acrylate (D) which is a reaction product of a thiol compound (A) having two or more mercapto groups; an iso(thio)cyanate compound (B) having two or more iso(thio)cyanato groups; and a hydroxy (meth)acrylate compound (C) having one or more polymerizable groups.

1 . A method for producing a monomer composition, comprising the steps of:
 (i) reacting a thiol compound (A) having two or more mercapto groups with an iso(thio)cyanate compound (B) having two or more iso(thio)cyanato groups to obtain an intermediate; and   (ii) reacting the intermediate with a hydroxy (meth)acrylate compound (C) having one or more polymerizable groups,   wherein a ratio (a/b) of the number of moles of the mercapto groups of the thiol compound (A), a, to the number of moles of the iso(thio)cyanato groups of the iso(thio)cyanate compound (B), b, preferably 0.01 to 0.20 in the step (i); and   the monomer composition comprises a (meth)acrylate (D) represented by the following general formula (1):   
       
         
           
           
               
               
           
         
       
       wherein
 R 1  is a residue excluding all mercapto groups from a thiol compound (A1) having three or four mercapto groups; 
 R 2  is a residue excluding all iso(thio)cyanato groups from an iso(thio)cyanate compound (B1) having two iso(thio)cyanato groups; 
 R 3  is a residue excluding one (meth)acryloyloxy group and one hydroxy group from the hydroxy (meth)acrylate compound (C); 
 R 4  represents a hydrogen atom or a methyl group; 
 X represents an oxygen atom or a sulfur atom: 
 n represents the number of all the mercapto groups contained in the thiol compound (A1); and 
 a plurality of R 2 , R 3 , R 4 , and X may each be the same as or different from each other. 
 
     
     
         2 . The method for producing a monomer composition according to  claim 1 , wherein in the general formula (1), R 1  has a molecular weight of 150 to 400. 
     
     
         3 . The method for producing a monomer composition according to  claim 1 , wherein in the general formula (1), R 1  is a group represented by the following formula (2), (3), (4-1), (4-2), or (4-3): 
       
         
           
           
               
               
           
         
       
     
     
         4 . The method for producing a monomer composition according to  claim 1 , wherein in the general formula (1), R 2  is a group represented by the following formula (5), (6), (7), or (8) 
       
         
           
           
               
               
           
         
       
     
     
         5 . The method for producing a monomer composition according to  claim 1 , wherein the thiol compound (A) is at least one selected from the group consisting of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 1,1,3,3-tetrakis(mercaptomethylthio)propane. 
     
     
         6 . The method for producing a monomer composition according to  claim 1 , wherein the iso(thio)cyanate compound (B) is at least one selected from the group consisting of hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate. 
     
     
         7 . A dental therapeutic method comprising a step of polymerizing inside the mouth a dental material composition comprising a polymerization initiator and a monomer composition comprising a (meth)acrylate (D) represented by the following general formula (1) to obtain a cured material: 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  is a residue excluding all mercapto groups from a thiol compound (A1) having three or four mercapto groups; 
 R 2  is a residue excluding all iso(thio)cyanato groups from an iso(thio)cyanate compound (B1) having two iso(thio)cyanato groups; 
 R 3  is a residue excluding one (meth)acryloyloxy group and one hydroxy group from the hydroxy (meth)acrylate compound (C); 
 R 4  represents a hydrogen atom or a methyl group; 
 X represents an oxygen atom or a sulfur atom: 
 n represents the number of all the mercapto groups contained in the thiol compound (A1); and 
 a plurality of R 2 , R 3 , R 4 , and X may each be the same as or different from each other. 
 
     
     
         8 . The dental therapeutic method according to  claim 7 , wherein in the general formula (1), R 1  has a molecular weight of 150 to 400. 
     
     
         9 . The dental therapeutic method according to  claim 7 , wherein in the general formula (1), R 1  is a group represented by the following formula (2), (3), (4-1), (4-2), or (4-3): 
       
         
           
           
               
               
           
         
       
     
     
         10 . The dental therapeutic method according to  claim 7 , wherein in the general formula (1), R 2  is a group represented by the following formula (5), (6), (7), or (8): 
       
         
           
           
               
               
           
         
       
     
     
         11 . The dental therapeutic method according to  claim 7 , wherein the thiol compound (A) is at least one selected from the group consisting of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 1,1,3,3-tetrakis(mercaptomethylthio)propane. 
     
     
         12 . The dental therapeutic method according to  claim 7 , wherein the iso(thio)cyanate compound (B) is at least one selected from the group consisting of hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate. 
     
     
         13 . A dental therapeutic method comprising the steps of:
 polymerizing outside the mouth a dental material composition comprising a polymerization initiator and a monomer composition comprising a (meth)acrylate (D) represented by the following general formula (1) to obtain a cured product:   
       
         
           
           
               
               
           
         
       
       wherein
 R 1  is a residue excluding all mercapto groups from a thiol compound (A1) having three or four mercapto groups; 
 R 2  is a residue excluding all iso(thio)cyanato groups from an iso(thio)cyanate compound (B1) having two iso(thio)cyanato groups; 
 R 3  is a residue excluding one (meth)acryloyloxy group and one hydroxy group from the hydroxy (meth)acrylate compound (C); 
 R 4  represents a hydrogen atom or a methyl group; 
 X represents an oxygen atom or a sulfur atom: 
 n represents the number of all the mercapto groups contained in the thiol compound (A1); and 
 a plurality of R 2 , R 3 , R 4 , and X may each be the same as or different from each other, and 
 applying the cured product inside the mouth. 
 
     
     
         14 . The dental therapeutic method according to  claim 13 , wherein in the general formula (1), R 1  has a molecular weight of 150 to 400. 
     
     
         15 . The dental therapeutic method according to  claim 13 , wherein in the general formula (1), R 1  is a group represented by the following formula (2), (3), (4-1), (4-2), or (4-3): 
       
         
           
           
               
               
           
         
       
     
     
         16 . The dental therapeutic method according to  claim 13 , wherein in the general formula (1), R 2  is a group represented by the following formula (5), (6), (7), or (8): 
       
         
           
           
               
               
           
         
       
     
     
         17 . The dental therapeutic method according to  claim 13 , wherein the thiol compound (A) is at least one selected from the group consisting of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 1,1,3,3-tetrakis(mercaptomethylthio)propane. 
     
     
         18 . The dental therapeutic method according to  claim 13 , wherein the iso(thio)cyanate compound (B) is at least one selected from the group consisting of hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate.